EP1358273B1 - Phthalimidyl azo dyes, process for their preparation and the use thereof - Google Patents

Phthalimidyl azo dyes, process for their preparation and the use thereof Download PDF

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Publication number
EP1358273B1
EP1358273B1 EP02711819A EP02711819A EP1358273B1 EP 1358273 B1 EP1358273 B1 EP 1358273B1 EP 02711819 A EP02711819 A EP 02711819A EP 02711819 A EP02711819 A EP 02711819A EP 1358273 B1 EP1358273 B1 EP 1358273B1
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EP
European Patent Office
Prior art keywords
formula
dye
sub
alkyl
synthetic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02711819A
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German (de)
English (en)
French (fr)
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EP1358273A1 (en
Inventor
Antoine Clement
Jean-Claude Wilhelm
Alfons Arquint
Urs Lauk
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Huntsman Advanced Materials Switzerland GmbH
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Huntsman Advanced Materials Switzerland GmbH
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Publication date
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Priority to EP02711819A priority Critical patent/EP1358273B1/en
Publication of EP1358273A1 publication Critical patent/EP1358273A1/en
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Publication of EP1358273B1 publication Critical patent/EP1358273B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
    • C09B29/0033—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a five-membered heterocyclic ring with one nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • C09B29/0813—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by OH, O-C(=X)-R, O-C(=X)-X-R, O-R (X being O,S,NR; R being hydrocarbonyl)

Definitions

  • the present invention relates to disperse dyes having an N-methyl-phthalimide-diazo component and an aniline coupling component, to processes for the preparation of such dyes and to the use thereof in dyeing or printing semi-synthetic and especially synthetic hydrophobic fibre materials, especially textile materials.
  • Disperse azo dyes having an N-alkyl-phthalimide-diazo component and an aniline coupling component have been known for a long time, for instance from U.S. Patent No. 3,980,634 , or WO 00/40656 , and are used in dyeing hydrophobic fibre materials. It has, however, been found that the dyeings or prints obtained using the currently known dyes do not in all cases satisfy today's requirements, especially in respect of fastness to washing and fastness to perspiration. There is therefore a need for new dyes that especially have good washing fastness properties.
  • the present invention accordingly relates to disperse dyes that yield dyeings having a high degree of fastness to washing and to perspiration and that, in addition, have good build-up characteristics both in the exhaust and thermosol processes and in textile printing.
  • the dyes are also suitable for discharge printing.
  • the dyes according to the invention correspond to formula wherein R is hydrogen or bromine, R 1 is hydrogen, methyl or -NHCO-C 1 -C 4 alkyl, R 2 is C 1 -C 4 alkyl substituted by C 1 -C 4 alkoxy and R 3 has, independently of R 2 , any of the meanings of R 2 .
  • R 1 is preferably -NHCO-C 1 -C 4 alkyl.
  • C 1 -C 4 Alkyl in the radical -NHCO-C 1 -C 4 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, especially methyl.
  • R 2 and R 3 as C 1 -C 4 alkyl are, each independently of the other, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • R 2 and R 3 preferably have the same meaning.
  • R 2 and R 3 are especially ethyl.
  • C 1 -C 4 Alkoxy as substituent of C 1 -C 4 alkyl in R 2 and R 3 is, for example, methoxy, ethoxy or propoxy, especially methoxy.
  • the present invention relates also to the process for the preparation of the dyes of formula (1) according to the invention.
  • the dyes are prepared, for example, by nitration of a phthalimide of formula in the acid range, as described, for example, on page 459 in Organic Synthesis, Collective Volume 2, (a Revised Edition of Annual Volumes X-XIX), J.Wiley & Sons , followed by alkylation of the resulting nitro compound, for example in accordance with a method described in Journal of Organic Chemistry 32 (1967) on page 1923 , paragraph 3, and, for example after reductive treatment described in Bull. Soc. Chim. de France 1957 on page 569 , conversion into an intermediate of formula
  • the intermediate of formula (51) is mono- or di-halogenated and the resulting compound is then, in an acid medium, diazotised and coupled to a compound of formula wherein R 1 , R 2 and R 3 have the definitions and preferred meanings given above.
  • the halogenation is carried out, for example, by reacting the compound of formula (51) first with sodium acetate in acetic acid and then with bromine in the same medium to form the corresponding mono- or di-bromo compound.
  • the diazotisation of the compound of formula (51) is likewise carried out in a manner known per se, for example with sodium nitrite in an acidic, for example hydrochloric-acid-containing or sulfuric-acid-containing, aqueous medium.
  • the diazotisation may, however, also be carried out using other diazotisation agents, e.g. with nitrosylsulfuric acid.
  • an additional acid may be present in the reaction medium, e.g. phosphoric acid, sulfuric acid, acetic acid, propionic acid, hydrochloric acid or mixtures of such acids, e.g. mixtures of propionic acid and acetic acid.
  • the diazotisation is advantageously carried out at temperatures of from -10 to 30°C, for example from -10°C to room temperature.
  • the coupling of the diazotised compound of formula (51) to the coupling component of formula (52) is likewise effected in known manner, for example in an acidic, aqueous or aqueous-organic medium, advantageously at temperatures of from -10 to 30°C, especially below 10°C.
  • acids used are hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid.
  • the diazo components of formula (51) and the coupling components of formula (52) are known or can be prepared in a manner known per se.
  • the present invention relates also to dye mixtures comprising at least one azo dye of formula (1) and at least one azo dye of formula wherein R 1 is hydrogen, methyl or -NHCO-C 1 -C 4 alkyl, R 2 is C 1 -C 4 alkyl, it being possible for the alkyl chain, from C 2 upwards, optionally to be interrupted by an oxygen atom, and R 3 has, independently of R 2 , any of the meanings of R 2 .
  • dye mixtures that comprise at least one azo dye of formula (1) and the azo dyes of formulae and
  • the azo dyes of formulae (4), (5) and (6) can be prepared analogously to known compounds using generally known methods.
  • the azo dyes of formula (4) used in accordance with the invention are prepared, for example, by nitration of a phthalimide of formula in the acid range, as described, for example, on page 459 in Organic Synthesis, Collective Volume 2, (a Revised Edition of Annual Volumes X-XIX), J.Wiley & Sons , followed by alkylation of the resulting nitro compound, for example in accordance with a method described in Journal of Organic Chemistry 32 (1967) on page 1923 , paragraph 3, and, for example after reductive treatment described on page 569 in Bull. Soc. Chim. de France 1957 , conversion into an intermediate of formula
  • the intermediate of formula (53) is dihalogenated and then, in an acid medium, diazotised and coupled to a compound of formula wherein R 1 , R 2 and R 3 have the definitions and preferred meanings given above.
  • the reaction to form the final dyes is carried out by replacement of the two bromine atoms by cyano groups using methods known per se, for example using CuCN or mixtures of CuCN and an alkali metal cyanide in a solvent, for example dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-vinylpyrrolidone, sulfolane or pyridine.
  • a solvent for example dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-vinylpyrrolidone, sulfolane or pyridine.
  • the halogenation is carried out, for example, by reacting the compound of formula (53) first with sodium acetate in acetic acid and then with bromine in the same medium to form the corresponding di-bromo compound.
  • the diazotisation of the compound of formula (53) is likewise carried out in a manner known per se, for example with sodium nitrite in an acidic, for example hydrochloric-acid-containing or sulfuric-acid-containing, aqueous medium.
  • the diazotisation may, however, also be carried out using other diazotisation agents, e.g. with nitrosylsulfuric acid.
  • an additional acid may be present in the reaction medium, e.g. phosphoric acid, sulfuric acid, acetic acid, propionic acid, hydrochloric acid or mixtures of such acids, e.g. mixtures of propionic acid and acetic acid.
  • the diazotisation is advantageously carried out at temperatures of from -10 to 30°C, for example from -10°C to room temperature.
  • the coupling of the diazotised compound of formula (53) to the coupling component of formula (54) is likewise effected in known manner, for example in an acidic, aqueous or aqueous-organic medium, advantageously at temperatures of from -10 to 30°C, especially below 10°C.
  • acids used are hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid.
  • the diazo components of formula (53) and the coupling components of formula (54) are known or can be prepared in a manner known per se.
  • the dye mixtures according to the invention comprising the azo dyes defined hereinbefore can be prepared, for example, by simply mixing the individual dyes, for example by mixing the azo dyes of formulae (2), (5) and (6).
  • the amounts of the individual dyes in the dye mixtures according to the invention can vary within a wide range, for example from from 30 to 55 parts by weight, especially from 34 to 50 parts by weight, of the azo dye of formula (1) to from 45 to 70 parts by weight, especially from 50 to 66 parts by weight, of the azo dye of formula (4), based on 100 parts by weight of the dye mixture according to the invention.
  • the dye mixtures according to the invention preferably contain from 34 to 50 % by weight of the azo dye of formula (2), from 25 to 33 % by weight of the azo dye of formula (5) and from 25 to 33 % by weight of the azo dye of formula (6), based on 100 % by weight of the dye mixture according to the invention.
  • the dyes and dye mixtures according to the invention may be used for dyeing or printing semi-synthetic and especially synthetic hydrophobic fibre materials, especially textile materials.
  • Textile materials composed of blend fabrics that comprise such semi-synthetic or synthetic hydrophobic fibre materials can also be dyed or printed using the dyes or dye mixtures according to the invention.
  • Semi-synthetic fibre materials that come into consideration are, especially, cellulose 21 ⁇ 2-acetate and cellulose triacetate.
  • Synthetic hydrophobic fibre materials consist especially of linear, aromatic polyesters, for example those of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, e.g. those of ⁇ , ⁇ -dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, and of fibres based on polyvinyl chloride and on polyamide.
  • polyester fibre materials are dyed in the exhaust process from an aqueous dispersion in the presence of customary anionic or non-ionic dispersants and, optionally, customary swelling agents (carriers) at temperatures of from 80 to 140°C.
  • customary anionic or non-ionic dispersants and, optionally, customary swelling agents (carriers) at temperatures of from 80 to 140°C.
  • Cellulose 21 ⁇ 2-acetate is dyed preferably at from 65 to 85°C and cellulose triacetate at temperatures of from 65 to 115°C.
  • the dyes and dye mixtures according to the invention will not colour wool and cotton present at the same time in the dyebath or will colour such materials only slightly (very good reservation) so that they can also be used satisfactorily in the dyeing of polyester/wool and polyester/cellulosic fibre blend fabrics.
  • the dyes and dye mixtures according to the invention are suitable for dyeing in accordance with the thermosol process, in the exhaust process and for printing processes.
  • the said fibre materials can be in a variety of processing forms, e.g. in the form of fibres, yarns or nonwoven, woven or knitted fabrics.
  • the dye is ground so that its particle size is on average from 0.1 to 10 microns. Grinding can be carried out in the presence of dispersants. For example, the dried dye is ground together with a dispersant or kneaded into a paste form together with a dispersant and then dried in vacuo or by atomisation. After adding water, the resulting preparations can be used to prepare printing pastes and dyebaths.
  • the customary thickeners will be used, e.g. modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, locust bean flour, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols.
  • modified or unmodified natural products for example alginates, British gum, gum arabic, crystal gum, locust bean flour, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols.
  • the dyes and dye mixtures according to the invention impart to the said materials, especially to polyester materials, level colour shades having very good in-use fastness properties such as, especially, good fastness to light, fastness to heat setting, fastness to pleating, fastness to chlorine, and wet fastness, e.g. fastness to water, to perspiration and to washing; the finished dyeings are further characterised by very good fastness to rubbing. Special emphasis should be given to the good fastness properties of the dyeings obtained with respect to perspiration and, especially, to washing.
  • the dyes and dye mixtures according to the invention can also be used satisfactorily in producing mixed shades together with other dyes.
  • the dyes and dye mixtures according to the invention are also well suited to dyeing hydrophobic fibre materials from supercritical CO 2 .
  • the present invention relates to the above-mentioned use of the dyes and dye mixtures according to the invention as well as to a process for the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials, especially textile materials, in which process a dye according to the invention is applied to the said materials or incorporated into them.
  • the said hydrophobic fibre materials are preferably textile polyester materials. Further substrates that can be treated by the process according to the invention and preferred process conditions can be found above in the more detailed description of the use of the dyes according to the invention.
  • the invention relates also to hydrophobic fibre materials, preferably polyester textile materials, dyed or printed by the said process.
  • the dyes according to the invention are, in addition, suitable for modern reproduction processes, e.g. thermotransfer printing.
  • the mixture is added dropwise, over the course of 10 minutes, to a mixture consisting of 6.30 g of glacial acetic acid, 0.58 g of 32 % hydrochloric acid, 11.00 g of ice-water and 5.00 g of a 31.1 % aqueous solution of the compound of formula at a temperature of 0-5°C and is stirred for 120 minutes. Then, over the course of 10 minutes, 15.00 g of ice-water are added dropwise; the resulting red suspension is filtered with suction, washed with deionised water and dried.
  • 1 part by weight of the dye of formula is ground in a sand mill, together with 17 parts by weight of water and 2 parts by weight of a commercially available dispersant of the dinaphthylmethanedisulfonate type, and converted into a 5 % aqueous dispersion.
  • a 1 % dyeing (based on the dye and the substrate) is produced on woven polyester fabric by the high-temperature exhaust process at 130°C and is cleaned reductively.
  • the red-brown dyeing obtained in that manner has very good in-use fastness properties, especially excellent fastness to washing.
  • thermosol process 10 g/litre of dye, liquor pick-up 50 %, fixing temperature 210°C.
  • a 1 % dyeing (based on the dye and the substrate) is produced on woven polyester fabric by the high-temperature exhaust process at 130°C and is cleaned reductively.
  • the brown-black dyeing obtained in that manner has very good in-use fastness properties, especially excellent fastness to washing.
  • thermosol process 10 g/litre of dye, liquor pick-up 50 %, fixing temperature 210°C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP02711819A 2001-02-07 2002-01-29 Phthalimidyl azo dyes, process for their preparation and the use thereof Expired - Lifetime EP1358273B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02711819A EP1358273B1 (en) 2001-02-07 2002-01-29 Phthalimidyl azo dyes, process for their preparation and the use thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP01810128 2001-02-07
EP01810128 2001-02-07
PCT/EP2002/000903 WO2002074864A1 (en) 2001-02-07 2002-01-29 Phthalimidyl azo dyes, process for the preparation thereof and the use thereof
EP02711819A EP1358273B1 (en) 2001-02-07 2002-01-29 Phthalimidyl azo dyes, process for their preparation and the use thereof

Publications (2)

Publication Number Publication Date
EP1358273A1 EP1358273A1 (en) 2003-11-05
EP1358273B1 true EP1358273B1 (en) 2010-11-24

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EP02711819A Expired - Lifetime EP1358273B1 (en) 2001-02-07 2002-01-29 Phthalimidyl azo dyes, process for their preparation and the use thereof

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US (1) US7012137B2 (enrdf_load_stackoverflow)
EP (1) EP1358273B1 (enrdf_load_stackoverflow)
JP (1) JP4260483B2 (enrdf_load_stackoverflow)
KR (1) KR100868666B1 (enrdf_load_stackoverflow)
CN (1) CN1289607C (enrdf_load_stackoverflow)
AT (1) ATE489432T1 (enrdf_load_stackoverflow)
CZ (1) CZ20032382A3 (enrdf_load_stackoverflow)
DE (1) DE60238388D1 (enrdf_load_stackoverflow)
ES (1) ES2354500T3 (enrdf_load_stackoverflow)
PL (1) PL362776A1 (enrdf_load_stackoverflow)
RU (1) RU2283328C2 (enrdf_load_stackoverflow)
WO (1) WO2002074864A1 (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101035841B1 (ko) * 2002-11-11 2011-05-20 시바 홀딩 인크 프탈이미딜-아조 염료 및 이의 제조 방법
KR20050085747A (ko) * 2002-12-19 2005-08-29 시바 스페셜티 케미칼스 홀딩 인크. 프탈이미딜 아조 염료, 이의 제조방법 및 이의 용도
DE102006027535A1 (de) * 2006-06-14 2007-12-20 Dystar Textilfarben Gmbh & Co. Deutschland Kg Dispersionsfarbstoffe, ihre Herstellung und ihre Verwendung
CN102876068B (zh) * 2012-10-22 2015-08-12 浙江万丰化工有限公司 一种邻苯二甲酰亚胺基偶氮染料的制备方法
EP2754696A1 (en) 2013-01-15 2014-07-16 DyStar Colours Distribution GmbH AOX-free navy and black disperse dye mixtures
MX373638B (es) 2013-01-14 2020-05-04 Dystar Colours Distrib Gmbh Mezclas de tinturas dispersas de alta solidez en humedo.
CN103965094B (zh) * 2013-01-31 2016-07-06 江苏道博化工有限公司 N-甲基-4-氨基-5-溴-邻苯二甲酰亚胺的合成方法
CN105647224A (zh) * 2016-01-28 2016-06-08 俞杏英 一种邻苯二甲酰亚胺-偶氮分散染料单体化合物及其制备方法和应用
ES2814375T3 (es) 2017-10-02 2021-03-26 Dystar Colours Distrib Gmbh Mezclas de colorantes de dispersión rápida con alta humedad

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980634A (en) 1973-07-02 1976-09-14 Eastman Kodak Company Phthalimidyl-azo aniline type compounds and polyester fibers dyed therewith
JPS5818470B2 (ja) * 1974-09-06 1983-04-13 三菱化学株式会社 ゴウセイセンイルイ ノ センシヨクホウホウ
EP0443984B1 (de) * 1990-02-19 1995-01-18 Ciba-Geigy Ag Phthalimidyl-Azofarbstoffe
TWI243192B (en) 1998-12-31 2005-11-11 Ciba Sc Holding Ag Phthalimidyl azo pigments, method for producing same and utilization thereof

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Publication number Publication date
KR20030072400A (ko) 2003-09-13
RU2283328C2 (ru) 2006-09-10
US20040116681A1 (en) 2004-06-17
ES2354500T3 (es) 2011-03-15
ATE489432T1 (de) 2010-12-15
WO2002074864A1 (en) 2002-09-26
RU2003125651A (ru) 2005-03-20
CZ20032382A3 (cs) 2003-11-12
KR100868666B1 (ko) 2008-11-13
PL362776A1 (en) 2004-11-02
JP2004528435A (ja) 2004-09-16
CN1289607C (zh) 2006-12-13
US7012137B2 (en) 2006-03-14
EP1358273A1 (en) 2003-11-05
DE60238388D1 (de) 2011-01-05
CN1491258A (zh) 2004-04-21
JP4260483B2 (ja) 2009-04-30

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